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Nickel(II) complexes with covalently attached quinols rely on ligand-derived redox couples to catalyze superoxide dismutation

https://doi.org/10.1039/d4dt03331k

Boothe, Robert; Oppelt, Julian; Franke, Alicja; Moore, Jamonica L; Squarcina, Andrea; Zahl, Achim; Senft, Laura; Kellner, Ina; Awalah, Akudo L; Bradford, Alisabeth; et al (February 2025, Dalton Transactions)

Although nickel is found in the active sites of a class of superoxide dismutase (SOD), nickel complexes with non-peptidic ligands normally do not catalyze superoxide degradation, and none has displayed activity comparable to those of the best manganese-containing SOD mimics. Here, we find that nickel complexes with polydentate quinol-containing ligands can exhibit catalytic activity comparable to those of the most efficient manganese-containing SOD mimics. The nickel complexes retain a significant portion of their activity in phosphate buffer and under operando conditions and rely on ligand-centered redox processes for catalysis. Although nickel SODs are known to cycle through Ni(II) and Ni(III) species during catalysis, cryo-mass spectrometry studies indicate that the nickel atoms in our catalysts remain in the +2 oxidation state throughout SOD mimicry.
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Free, publicly-accessible full text available February 25, 2026
A macrocyclic quinol-containing ligand enables high catalase activity even with a redox-inactive metal at the expense of the ability to mimic superoxide dismutase

https://doi.org/10.1039/d3sc02398b

Karbalaei, Sana; Franke, Alicja; Oppelt, Julian; Aziz, Tarfi; Jordan, Aubree; Pokkuluri, P Raj; Schwartz, Dean D; Ivanović-Burmazović, Ivana; Goldsmith, Christian R (September 2023, Chemical Science)

Manganese, iron, and zinc complexes with the macrocyclic quinol-containing ligand H₄qp4 are highly active and durable catalysts for the dismutation of hydrogen peroxide but do not efficiently dismutate superoxide.
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Diquinol Functionality Boosts the Superoxide Dismutase Mimicry of a Zn(II) Complex with a Redox-Active Ligand while Maintaining Catalyst Stability and Enhanced Activity in Phosphate Solution

https://doi.org/10.1021/acs.inorgchem.2c03256

Moore, Jamonica L.; Oppelt, Julian; Senft, Laura; Franke, Alicja; Scheitler, Andreas; Dukes, Meghan W.; Alix, Haley B.; Saunders, Alexander C.; Karbalaei, Sana; Schwartz, Dean D.; et al (December 2022, Inorganic Chemistry)

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Superoxide dismutase activity enabled by a redox-active ligand rather than metal

https://doi.org/10.1038/s41557-018-0137-1

Ward, Meghan B.; Scheitler, Andreas; Yu, Meng; Senft, Laura; Zillmann, Annika S.; Gorden, John D.; Schwartz, Dean D.; Ivanović-Burmazović, Ivana; Goldsmith, Christian R. (December 2018, Nature Chemistry)

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